TW201739791A - Polyamide acid, thermoplastic polyimide, resin film, metal-clad laminate and circuit board - Google Patents

Abstract

A polyamide acid which contains at least one diamine compound selected from among diamine compounds represented by general formula (8) within the range of 3-60 parts by mole in total per 100 parts by mole of all diamine components, while containing a biphenyl tetracarboxylic acid dianhydride within the range of 40-100 parts by mole and a pyromellitic acid dianhydride within the range of 0-60 parts by mole per 100 parts by mole of all acid anhydride components; and a thermoplastic polyimide which is obtained curing this polyamide acid. (In formula (8), linking group X represents a single bond or a divalent group selected from among -CONH-; each Y independently represents a hydrogen atom, a monovalent hydrocarbon group having 1-3 carbon atoms or an alkoxy group; n represents an integer of 0-2; and each of p and q independently represents an integer of 0-4.)

Description

Polylysine, thermoplastic polyimide, resin film, metal coated laminate and circuit substrate

The present invention relates to a polyimide which can be used as an adhesive layer in a circuit board such as a flexible printed wiring board and the use thereof.

In recent years, with the advancement of miniaturization, weight reduction, and space saving of electronic equipment, flexible printed wiring boards (FPC: Flexible Printed) which are thin, lightweight, flexible, and excellent in durability even if they are repeatedly bent. The demand for Circuits) has increased. FPC can also perform stereoscopic and high-density installation in a limited space, for example, in Hard Disk Drive (HDD), Digital Versatile Disc (DVD), mobile phones and other electronic devices. The wiring of the movable part, or parts such as cables and connectors are constantly expanding their use.

With the increase in density, the narrow pitch of the wiring in the FPC advances, requiring fine processing. Here, as a wiring material, if a general copper foil is not used, the fine wiring processing is difficult. Further, when the surface roughness of the copper foil is large, the surface roughness is transferred to the side of the insulating layer. Therefore, in the region where the copper foil is removed by etching, the surface of the insulating layer may diffusely reflect light and pass through the insulating layer. A problem with the copper pattern was identified.

In addition, since the performance of the device is advanced, it is necessary to respond to the high frequency of the transmission signal. In the information processing or information communication, in order to increase the transmission frequency in order to transmit and process large-capacity information, it is required to reduce the thickness of the insulating layer and the low dielectric constant of the insulating layer for the circuit board material. A decrease in transmission loss caused by low dielectric loss tangential. In the conventional FPC using polyimine, since the dielectric constant or the dielectric loss tangent is high, the transmission loss in the high frequency domain is high, so that it is difficult to adapt to high frequency transmission. Therefore, in order to cope with high frequency, a liquid crystal polymer characterized by a low dielectric constant and a low dielectric loss tangent is used as the FPC of the dielectric layer. However, although the liquid crystal polymer is excellent in dielectric properties, there is room for improvement in heat resistance or adhesion to a metal foil.

For the purpose of improving the dielectric properties and improving the adhesion to the metal foil, a copper-clad laminate in which the concentration of the quinone imine of the polyimide layer in contact with the copper foil forming the conductor circuit is controlled is proposed. Board (Patent Document 1). According to Patent Document 1, the combination of the surface roughness Rz of the copper foil and the polyamidimine layer having a low fluorinated imine concentration on the surface in contact with the copper foil can control dielectric properties but long-term heat-resistant adhesion. Not fully satisfactory.

In order to improve the adhesion between the low-roughness copper foil and the insulating layer, a copper foil in which a predetermined metal is deposited on the surface of the copper foil that is in contact with the insulating layer has been proposed (Patent Document 2). According to Patent Document 2, by controlling the amount of precipitation of nickel, zinc, and cobalt, it is possible to ensure the initial adhesion and the decrease in the adhesion after the heat resistance test. However, since the copper foil of the patent document 2 is a non-thermoplastic polyimide resin, the adhesion of the copper foil by the lamination method is difficult, and the manufacturing method or manufacturing conditions are limited. [Prior Art Literature] Patent Literature

Patent Document 1: Japanese Patent No. 5031639 Patent Document 2: Japanese Patent No. 4652020

[Problems to be Solved by the Invention] In the high-density mounting of the FPC, in order to achieve not only the correspondence between the fine processing of the wiring but also the diffuse reflection of the light on the surface of the insulating layer in the region where the copper foil is etched away, it is effective. A copper foil having a small surface roughness is used. Further, in a state where a high-frequency signal is supplied to the signal wiring, a current flows only on the surface of the signal wiring, the effective cross-sectional area of the current is reduced, and the DC resistance is increased, and a phenomenon of signal attenuation (skin effect) is known. By reducing the surface roughness of the surface of the copper foil in contact with the polyimide layer, it is possible to suppress an increase in the resistance of the signal wiring caused by the skin effect. However, when a low-roughness copper foil having a reduced surface roughness is used, there is a problem that the adhesion between the polyimide and the copper foil is impaired.

An object of the present invention is to provide a metal-clad laminate having a polyimide layer and a circuit substrate, wherein the polyimide layer has excellent adhesion to a metal layer such as copper foil and long-term heat resistance. The adhesion is improved, and the transmission loss can be reduced by reducing the dielectric loss tangent, and it can be suitably used for a circuit board for high frequency. [Means for solving the problem]

In order to solve the problem, the present inventors have found that by using a polyimide having a specific structure as an adhesive layer, it has excellent adhesion to a low-roughness copper foil and long-term heat-resistant adhesiveness. Moreover, low dielectric loss tangent can be performed to complete the present invention.

That is, the polylysine of the present invention is a polyamic acid obtained by reacting a diamine component with an anhydride component, wherein the diamine component is 100 moles of the total diamine component. At least one selected from the group consisting of the diamine compounds represented by the following general formulae (1) to (7) in a range of from 40 mol parts to 97 mol parts in total, and a total of 3 mol parts - At least one selected from the group consisting of diamine compounds represented by the following formula (8) in a range of 60 mole parts, and the acid anhydride component contains 40 mole parts per 100 mole parts of the total acid anhydride component Biphenyltetracarboxylic dianhydride in the range of up to 100 moles, and pyromellitic dianhydride in the range of 0 moles to 60 moles.

[Chemical 1] In the formulae (1) to (7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms; and the linking group A independently represents a group selected from -O-, -S-, -CO- a divalent group in -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-; n ₁ independently represents 0 to 4 An integer; except for the repetition of the formula (3) and the formula (2), except for the repetition of the formula (4) and the formula (4)]

[Chemical 2] [In the formula (8), the linking group X represents a divalent group selected from a single bond or -CONH-; Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms or an alkoxy group; and n represents 0 to 2 Integer; p and q independently represent integers from 0 to 4]

The thermoplastic polyimine of the present invention is a thermoplastic polyimine containing a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from an acid anhydride component, characterized by: relative to all diamine residues 100 mol parts of the base, containing at least one selected from the group consisting of the diamine compounds represented by the above formula (1) to formula (7) in a range of from 40 mol parts to 97 mol parts in total a diamine residue derived from the diamine residue, and a diamine residue selected from the group consisting of at least one of the diamine compounds represented by the formula (8) in a range of from 3 moles to 60 moles, and 100 moles of all tetracarboxylic acid residues, tetracarboxylic acid residues derived from biphenyltetracarboxylic dianhydride in the range of 40 to 100 moles, and 0 moles - A tetracarboxylic acid residue derived from pyromellitic dianhydride in the range of 60 moles.

The resin film of the present invention is a resin film having a single layer or a plurality of layers of a polyimide layer, wherein at least one layer of the polyimide layer contains the thermoplastic polyimide.

The metal-clad laminate of the present invention is a metal-clad laminate comprising an insulating resin layer and a metal layer, wherein: the insulating resin layer has a single layer or a plurality of layers of polyimide, in contact with the metal layer The polyimide layer comprises the thermoplastic polyimine.

The ten-point average roughness (Rz) of the metal layer on the surface of the metal-clad laminate of the present invention which is in contact with the insulating resin layer may be in the range of 0.05 μm to 1.0 μm.

The circuit board of the present invention is obtained by processing the metal layer of the metal-clad laminate. [Effects of the Invention]

The thermoplastic polyimide of the present invention is excellent in adhesion, and has high adhesion to, for example, a low-roughness copper foil. Further, although the thermoplastic polyimide of the present invention is thermoplastic, since an ordered structure is formed in the entire polymer by using a rigid structure derived from a monomer, not only low dielectric loss tangent but also gas permeability can be obtained. Low, it can exhibit excellent long-term heat-resistant adhesion. Therefore, the resin film having the adhesive layer formed using the thermoplastic polyimide of the present invention is excellent in adhesion to the metal wiring layer. Further, by forming the thermoplastic polyimide layer using the thermoplastic polyimide of the present invention, low dielectric loss tangential can be performed. Therefore, the thermoplastic polyimide of the present invention can be suitably used as a material for producing electronic parts such as FPCs requiring high-density mounting or high-speed signal transmission and high reliability. Further, the metal-clad laminate using the thermoplastic polyimide of the present invention can be applied to, for example, a circuit board such as an FPC that transmits a high-frequency signal of 10 GHz or more.

Hereinafter, embodiments of the present invention will be described.

[Polyuric Acid and Thermoplastic Polyimine] <Polyuric Acid> The polyglycolic acid of the present embodiment is a precursor of the thermoplastic polyimine of the embodiment, and is a specific diamine component and an acid anhydride component. Obtained by carrying out the reaction.

<Thermoplastic Polyimine> The thermoplastic polyimide of the present embodiment is obtained by subjecting the polyamic acid to ruthenium iodide, and is produced by reacting a specific acid anhydride with a diamine. The acid anhydride and the diamine will be described to understand a specific example of the thermoplastic polyimide of the present embodiment.

(Diamine component) The diamine component of the raw material of the polyglycine of the present embodiment contains not only a total of 40 moles to 97 moles, but also a total of 100 moles of the total amount of the diamine component. At least one of the diamine compounds represented by the following general formulae (1) to (7), and further preferably in a range of from 3 moles to 60 moles, selected from the following formula (8) At least one of the diamine compounds represented.

[Chemical 3]

In the formulae (1) to (7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms; and the linking group A independently represents a group selected from -O-, -S-, -CO a divalent group in -, -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-; n ₁ independently represents 0 to 4 The integer. Wherein, the formula (3) is excluded from the formula (2), and the formula (5) is excluded from the formula (4). Here, "independently" means that one or more of the linking groups A, R ₁ or n ₁ may be used in one or both of the above formulas (1) to (7). The same or different.

[Chemical 4]

In the formula (8), the linking group X represents a divalent group selected from a single bond or -CONH-; Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms or an alkoxy group; n represents 0. An integer of ～2; p and q independently represent an integer of 0-4.

Further, in the formulae (1) to (8), a hydrogen atom in the two amine groups at the terminal may be substituted, and for example, may be -NR ₂ R ₃ (here, R ₂ and R ₃ independently refer to Any substituent such as an alkyl group).

When the diamine compound represented by the general formulae (1) to (7) is used in an amount within the above range, the flexibility of the molecular chain of the polyimine can be improved, and thermoplasticity can be imparted. When the total amount of the diamine compounds represented by the general formulae (1) to (7) is less than 40 mole parts per 100 parts by mole of the total diamine component, the flexibility of the polyimide resin is insufficient. If sufficient thermoplasticity is not obtained, if it exceeds 97 moles, the gas permeability is improved and the long-term heat resistance is lowered. The total amount of the diamine compounds represented by the general formulae (1) to (7) is preferably in the range of from 60 mole parts to 95 mole parts per 100 mole parts of all the diamine components.

In addition, by using the diamine compound represented by the general formula (8) in an amount within the above range, an ordered structure is formed in the entire polymer by using a rigid structure derived from a monomer, and therefore not only can be carried out The low dielectric loss is tangentially obtained, and a polyimide which is thermoplastic but has low gas permeability and long-term heat-resistant adhesiveness is obtained. When the total amount of the diamine compound represented by the formula (8) is less than 3 moles per 100 parts by mole of the total diamine component, it is difficult to form an ordered structure, and the effect is not exhibited. In the case of moles, the thermoplastic is damaged. The total amount of the diamine compound represented by the formula (8) is preferably in the range of 5 moles to 40 moles per 100 moles of the entire diamine component.

Therefore, the thermoplastic polyimine of the present embodiment contains a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from an acid anhydride component. Further, the thermoplastic polyimine of the present embodiment contains a total of from 40 mol parts to 97 mol parts in a range of from 100 mols to all the diamine residues, and is selected from the formula (1) a diamine residue derived from at least one of the diamine compounds represented by the formula (7), and a total of from 3 mol parts to 60 mol parts in a range selected from the formula (8) A diamine residue of at least one of the diamine compounds represented. Further, the thermoplastic polyimine of the present embodiment contains 40 parts by mole to 100 parts by mole of the biphenyltetracarboxylic dianhydride derived from 100 moles of all the tetracarboxylic acid residues. a tetracarboxylic acid residue, and a tetracarboxylic acid residue derived from pyromellitic dianhydride in the range of 0 moles to 60 moles.

The diamine (hereinafter, referred to as "diamine (1)") represented by the formula (1) is an aromatic diamine having two benzene rings. The diamine (1) is in a meta position by the amine group directly bonded to at least one benzene ring and the divalent linking group A, and the polyetherimine molecular chain has an increased degree of freedom and high flexibility. It is believed to contribute to the improvement of the flexibility of the polyimine molecular chain. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (1). Here, the linking group A is preferably -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, -S-.

Examples of the diamine (1) include 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenyl sulfide, and 3 , 3'-diaminodiphenylanthracene, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, (3,3'-diamino) Diphenylamine and the like.

The diamine (hereinafter, referred to as "diamine (2)") represented by the formula (2) is an aromatic diamine having three benzene rings. The diamine (2) is in a meta position by the amine group directly bonded to at least one benzene ring and the divalent linking group A, and the polyetherimine molecular chain has an increased degree of freedom and high flexibility. It is believed to contribute to the improvement of the flexibility of the polyimine molecular chain. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (2). Here, the linking group A is preferably -O-.

Examples of the diamine (2) include 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]aniline, and 3-[3- (4-Aminophenoxy)phenoxy]aniline or the like.

The diamine (hereinafter, referred to as "diamine (3)") represented by the formula (3) is an aromatic diamine having three benzene rings. The diamine (3) is in a meta position by two divalent linking groups A directly bonded to one benzene ring, and the degree of freedom of the polyimine molecular chain is increased to have high flexibility. It is believed to contribute to the improvement of the flexibility of the polyimine molecular chain. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (3). Here, the linking group A is preferably -O-.

Examples of the diamine represented by the formula (3) include 1,3-bis(4-aminophenoxy)benzene (TPE-R) and 1,3-bis(3-aminophenoxy)benzene ( APB), 4,4'-[2-methyl-(1,3-phenylene)dioxy]diphenylamine, 4,4'-[4-methyl-(1,3-phenylene) Dioxy]diphenylamine, 4,4'-[5-methyl-(1,3-phenylene)dioxy]diphenylamine, and the like.

The diamine (hereinafter, referred to as "diamine (4)") represented by the formula (4) is an aromatic diamine having four benzene rings. The diamine (4) has a high flexibility by being directly bonded to an amine group bonded to at least one benzene ring and a divalent linking group A, and is considered to contribute to the softness of the molecular chain of the polyimine. Sexual improvement. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (4). Here, the linking group A is preferably -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, -CONH-.

The diamine represented by the formula (4) may, for example, be bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]propane, or bis [ 4-(3-Aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)]diphenyl Methyl ketone, bis[4,4'-(3-aminophenoxy)]benzimidamide, and the like.

The diamine (hereinafter, referred to as "diamine (5)") represented by the formula (5) is an aromatic diamine having four benzene rings. The diamine (5) is in a meta position by two divalent linking groups A directly bonded to at least one benzene ring, and the poly-imine molecular chain has an increased degree of freedom and high flexibility. It is believed to contribute to the improvement of the softness of the molecular chain of polyimine. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (5). Here, the linking group A is preferably -O-.

The diamine (5) may, for example, be 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-benzene) Alkoxy)] diphenylamine and the like.

The diamine (hereinafter, referred to as "diamine (6)") represented by the formula (6) is an aromatic diamine having four benzene rings. The diamine (6) has high flexibility by having at least two ether bonds, and is considered to contribute to an improvement in flexibility of the polyimine molecular chain. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (6). Here, the linking group A is preferably -C(CH ₃ ) ₂ -, -O-, -SO ₂ -, -CO-.

Examples of the diamine represented by the formula (6) include 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and bis[4-(4-aminophenoxy). Phenyl]ether (BAPE), bis[4-(4-aminophenoxy)phenyl]indole (BAPS), bis[4-(4-aminophenoxy)phenyl]one (BAPK) Wait.

The diamine (hereinafter, referred to as "diamine (7)") represented by the formula (7) is an aromatic diamine having four benzene rings. Since the diamine (7) has a bivalent linking group A having high flexibility on both sides of the diphenyl skeleton, it is considered to contribute to an improvement in flexibility of the polyimine molecular chain. Therefore, the thermoplasticity of the polyimine is improved by using the diamine (7). Here, the linking group A is preferably -O-.

Examples of the diamine represented by the formula (7) include bis[4-(3-aminophenoxy)]biphenyl and bis[4-(4-aminophenoxy)]biphenyl.

The diamine (hereinafter, referred to as "diamine (8)") represented by the formula (8) is an aromatic diamine having one to three benzene rings. Since the diamine (8) has a rigid structure, it has an effect of imparting an ordered structure to the entire polymer. Therefore, by using one or more kinds of the diamines (1) to (II) and one or more kinds of the diamines (8) in combination at a predetermined ratio, not only the low dielectric loss tangential but also the obtained A polyimide which is thermoplastic but has low gas permeability and excellent long-term heat-resistant adhesion. Here, the linking group X is preferably a single bond, -CONH-.

Examples of the diamine (8) include p-phenylenediamine (PDA), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), and 2,2'-n-propyl group. -4,4'-diaminobiphenyl (m-NPB), 2'-methoxy-4,4'-diaminobenzimidamide (MABA), 4,4'-diaminobenzoic acid Anthranil (DABA) and the like.

(Acid anhydride) The acid anhydride component of the raw material of the polyamic acid of the present embodiment is contained in the range of 40 mol parts to 100 mol parts, preferably 50 mol parts to 100 parts per 100 parts by mole of the total acid anhydride component. Biphenyltetracarboxylic dianhydride in the range of moles, and pyromellitic acid in the range of 0 moles to 60 moles, preferably 0 moles to 50 moles anhydride. Here, examples of the biphenyltetracarboxylic dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride and 2,3',3,4'-biphenyltetracarboxylic dianhydride. 2,2',3,3'-biphenyltetracarboxylic dianhydride, and the like. By using biphenyltetracarboxylic dianhydride in the above range, an ordered structure due to a rigid structure is formed, so that not only low dielectric loss tangent, but also thermoplasticity, but low gas permeability, Polyimine which is excellent in long-term heat-resistant adhesion. When the biphenyltetracarboxylic dianhydride is less than 40 mol parts, it is difficult to form an ordered structure, and the effect is not exhibited. Further, pyromellitic dianhydride is an optional component, but is a monomer which functions to control the glass transition temperature.

In the present embodiment, other acid anhydrides other than the above may be included. Examples of the other acid anhydride include 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,2', 3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride , bis(2,3-dicarboxyphenyl)ether dianhydride, 3,3'', 4,4''-, 2,3,3'',4''- or 2,2'',3, 3''-Preference for triphenyltetracarboxylic dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3- or 3.4-dicarboxybenzene) Methane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)ruthenic anhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)ethane dianhydride 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-nonanedicarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6 , 7-(or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8-(or 2,3,6,7-)tetracarboxylic dianhydride, 2,3,8,9 -, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-anthracene-tetracarboxylic acid , cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid Dihydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride, 2,2-double [4 -(3,4-Dicarboxyphenoxy)phenyl]propane dianhydride or the like.

In the thermoplastic polyimine of the present embodiment, the thermal expansion property and the viscosity can be controlled by selecting the type of the acid anhydride and the diamine or the molar ratio of each of the two or more acid anhydrides or diamines. Connectivity, glass transition temperature (Tg), etc.

The thermoplastic polyimine of the present embodiment can be produced by reacting the diamine component and the acid anhydride component in a solvent to form a polyaminic acid, followed by heating and ring closure. For example, the acid anhydride component and the diamine component are dissolved in the organic solvent in substantially the same molar amount, and stirred at a temperature in the range of 0 ° C to 100 ° C for 30 minutes to 24 hours to carry out a polymerization reaction, thereby obtaining a polymerization. Polyproline of the precursor of quinone imine. In the reaction, the reaction component is dissolved so that the precursor formed in the range of 5 wt% to 30 wt%, preferably 10 wt% to 20 wt%, in the organic solvent. The organic solvent used in the polymerization reaction may, for example, be N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (N,N-dimethylacetamide). DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (dimethyl sulfoxide, DMSO), hexamethylphosphoniumamine, N-methyl caprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, Cresol and so on. These organic solvents may be used in combination of two or more kinds, and an aromatic hydrocarbon such as xylene or toluene may be used in combination. In addition, the amount of the organic solvent to be used is not particularly limited, and it is preferably adjusted so that the concentration of the polyaminic acid solution obtained by the polymerization reaction is about 5% by weight to 30% by weight.

The polylysine synthesized is generally advantageously used as a reaction solvent solution, and may be concentrated, diluted or substituted with other organic solvents as needed. Further, since polylysine is generally excellent in solvent solubility, it is advantageously used. The viscosity of the solution of polylysine is preferably in the range of 500 cP to 100,000 cps. When it is out of this range, when coating operation by a coater or the like is performed, defects such as thickness unevenness and streaking tend to occur on the film. The method for carrying out the hydrazine imidization of the poly-proline is not particularly limited, and for example, a heat treatment may be suitably employed: in the solvent, the temperature is in the range of 80 ° C to 400 ° C for 1 hour to 24 hours. Heating is carried out in an hour.

When the thermoplastic polyimide of the present embodiment is used, for example, as an adhesive layer in an insulating resin of a circuit board, in order to suppress the diffusion of copper, it is preferably a structure which is completely imidized. However, a part of the polyimine can be polylysine. The ruthenium imidization ratio is determined by using a Fourier transform infrared spectrophotometer (commercial product: FT/IR620 manufactured by JASCO Corporation), and the Attenuated Total Reflection (ATR) method is used to determine the polyimine. The infrared absorption spectrum of the film was calculated based on the absorbance of C=O stretching from the yttrium group of 1780 cm ^-1 based on the benzene ring absorber in the vicinity of 1015 cm ^-1 .

The weight average molecular weight of the thermoplastic polyimide of the present embodiment is, for example, preferably in the range of 10,000 to 400,000, more preferably in the range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the film tends to decrease and it tends to be brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity is excessively increased, and there is a tendency that defects such as film thickness unevenness and streaking tend to occur during the coating operation.

[Resin film] The resin film of the present embodiment is not particularly limited as long as it is a film containing an insulating resin of the polyimide layer formed of the thermoplastic polyimide of the present embodiment, and may be a film containing an insulating resin ( The sheet may be a film of an insulating resin in a state of being laminated on a substrate such as a copper foil, a glass plate, a polyimide film, a polyamide film, or a polyester film. Further, the thickness of the resin film of the present embodiment can be preferably in the range of 3 μm to 100 μm, and more preferably in the range of 3 μm to 75 μm.

Since the thermoplastic polyimide of the present embodiment has high expandability, it is suitably used as a bonding layer to a substrate such as a metal layer or another resin layer. In order to be suitable for use as the above-mentioned adhesive polyimide layer, the thermoplastic polyimide of the present embodiment preferably has a glass transition temperature (Tg) of, for example, 360 ° C or less, more preferably 200 ° C to ～ Within the range of 320 ° C.

When the thermoplastic polyimide of the present embodiment is used as an adhesive layer, for example, the coefficient of thermal expansion (CTE) may be 30 × 10 ^-6 (1/K) or less, preferably 10 × 10 ^{-6 .} A low thermal expansion polyimine layer in the range of ～30×10 ^-6 (1/K) is applied to the base film layer. Among the low thermal expansion polyimines, the polyimine which can be suitably used is a non-thermoplastic polyimine. The thickness of the base layer having a low thermal expansion property can be preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 35 μm.

When the thermoplastic polyimide of the present embodiment is applied as an adhesive layer of, for example, a circuit board, the dielectric loss tangent (Tan δ) at 10 GHz is preferably 0.004 or less. When the dielectric loss tangent at 10 GHz exceeds 0.004, when it is used on a circuit board such as an FPC, it is easy to cause a problem such as loss of an electric signal on a transmission path of a high-frequency signal. Further, the lower limit of the dielectric loss tangent at 10 GHz is not particularly limited.

When the thermoplastic polyimide of the present embodiment is applied as an adhesive layer of, for example, a circuit board, the dielectric constant at 10 GHz is preferably 4.0 or less in order to ensure impedance integration. When the dielectric constant at 10 GHz exceeds 4.0, when it is used on a circuit board such as an FPC, the dielectric loss is deteriorated, and a problem such as loss of an electric signal is likely to occur in the transmission path of the high-frequency signal.

The method for forming the polyimide film of the resin film of the present embodiment is not particularly limited, and examples thereof include: [1] coating a solution of polyglycolic acid on a support substrate and drying it, then performing imine a method for producing a polyimide film (hereinafter referred to as a casting method); [2] coating a solution of polyamic acid on a support substrate and drying the gel film of the poly-proline from the support group The material is peeled off, and a method of producing a polyimide film by hydrazine imidization is carried out. Further, in the case where the polyimine film produced in the present embodiment includes a plurality of layers of a polyimide resin layer, examples of the method for producing the film include, for example, [3] coating of a polyamide on a support substrate. After the solution of the amino acid and the drying operation are repeated a plurality of times, the method of ruthenium imidization (hereinafter referred to as sequential coating method); [4] on the supporting substrate, simultaneous coating by multi-layer extrusion After the laminated structure of valine acid is dried and dried, a method of ruthenium imidization (hereinafter referred to as a multilayer extrusion method) or the like is carried out. The method of applying the polyimine solution (or polylysine solution) to the substrate is not particularly limited, and for example, it can be applied by a coater such as a notch wheel, a die, a blade, a lip, or the like. In the case of forming a multilayered polyimide layer, it is preferred to carry out a method of applying a polyimine solution (or a polyamido acid solution) to a substrate and drying it.

The resin film of the present embodiment may comprise a single layer or a plurality of layers of a polyimide layer. In this case, at least one layer (preferably an adhesive layer) of the polyimide layer may be formed by using the thermoplastic polyimide of the present embodiment. For example, when the non-thermoplastic polyimide layer is P1 and the thermoplastic polyimide layer is P2, when the resin film is two layers, it is preferable to use a combination of P2/P1. When the resin film is formed into three layers, it is preferable to laminate the layers in the order of P2/P1/P2 or P2/P1/P1. Here, P1 is a base film layer formed using a non-thermoplastic polyimide, and P2 is an adhesive layer formed of the thermoplastic polyimide of the present embodiment.

The resin film of the present embodiment may contain an inorganic filler in the polyimide layer as needed. Specific examples thereof include cerium oxide, aluminum oxide, magnesium oxide, cerium oxide, boron nitride, aluminum nitride, cerium nitride, aluminum fluoride, and calcium fluoride. These may be used alone or in combination of two or more.

[Metal-clad laminate] The metal-clad laminate of the present embodiment includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer. A preferred example of the metal-clad laminate is, for example, a copper-clad laminate (CCL).

<Insulating Resin Layer> In the metal-clad laminate according to the present embodiment, the insulating resin layer has a single layer or a plurality of layers of a polyimide layer. In this case, at least one layer (preferably an adhesive layer) of the polyimide layer may be formed by using the thermoplastic polyimide of the present embodiment. Preferably, in order to improve the adhesion between the insulating resin layer and the metal layer, the layer in contact with the metal layer in the insulating resin layer is preferably an adhesive layer formed of the thermoplastic polyimide of the present embodiment. For example, when the insulating resin layer is two layers, it is preferable to set the non-thermoplastic polyimide layer to P1, the thermoplastic polyimide layer to P2, and the metal layer to M1. To layer in the order of P1/P2/M1. Here, P1 is a base film layer formed using any non-thermoplastic polyimide, and P2 is an adhesive layer composed of the thermoplastic polyimide of the present embodiment.

<Metal layer> The material of the metal layer in the metal-clad laminate according to the present embodiment is not particularly limited, and examples thereof include copper, stainless steel, iron, nickel, ruthenium, aluminum, zinc, indium, silver, gold, and tin. Zirconium, hafnium, titanium, lead, magnesium, manganese, and alloys thereof. Among them, copper or copper alloy is particularly preferred. Further, the material of the wiring layer in the circuit board of the present embodiment to be described later is also the same as that of the metal layer.

In a state where a high-frequency signal is supplied to the signal wiring, a current flows only on the surface of the signal wiring, and there is a problem that the effective cross-sectional area of the current flow decreases, the DC resistance increases, and the signal is attenuated (skin effect). By reducing the surface roughness of the surface of the metal layer such as the copper foil that is in contact with the insulating resin layer, it is possible to suppress an increase in the resistance of the signal wiring caused by the skin effect. However, when the surface roughness is lowered in order to suppress an increase in electric resistance, the adhesion (peeling strength) between the metal layer and the dielectric substrate is weak. Therefore, the surface roughness of the surface of the metal layer in contact with the insulating resin layer can be suppressed from the viewpoint of suppressing the increase in the electric resistance, ensuring the adhesion to the insulating resin layer, and improving the visibility of the metal-clad laminate. The ten-point average roughness Rz is preferably in the range of 0.05 μm to 1.0 μm, and preferably the arithmetic mean roughness Ra is 0.2 μm or less.

The metal-clad laminate can also be prepared by, for example, preparing a resin film comprising the thermoplastic polyimide of the present embodiment, after depositing a metal thereon to form a seed layer, for example, A metal layer is formed by plating.

Further, the metal-clad laminate can also be prepared by preparing a resin film comprising the thermoplastic polyimide of the present embodiment, and laminating the metal foil thereon by a method such as thermocompression bonding.

Further, the metal-clad laminate can also be prepared by casting a coating liquid containing polyamic acid, which is a precursor of the thermoplastic polyimide of the present embodiment, on a metal foil, and drying to form a coating film. Thereafter, heat treatment is carried out to imidize the oxime to form a polyimide layer.

[Circuit Substrate] The circuit board of the present embodiment includes an insulating resin layer and a wiring layer formed on the insulating resin layer. In the circuit board of the present embodiment, the insulating resin layer may have a single layer or a plurality of layers of a polyimide layer. In this case, in order to impart excellent high-frequency transmission characteristics to the circuit board, at least one layer (preferably an adhesive layer) of the polyimide layer may be formed by using the thermoplastic polyimide of the present embodiment. Further, in order to improve the adhesion between the insulating resin layer and the wiring layer, the layer in contact with the wiring layer in the insulating resin layer is preferably an adhesive layer formed using the thermoplastic polyimide of the present embodiment. For example, when the insulating resin layer is two layers, it is preferable to set the non-thermoplastic polyimide layer to P1, the thermoplastic polyimide layer to P2, and the wiring layer to M2. To stack in the order of P1/P2/M2. Here, P1 is a base film layer formed using any non-thermoplastic polyimide, and P2 is an adhesive layer formed of the thermoplastic polyimide of the present embodiment.

A method of producing a circuit board is used in addition to the thermoplastic polyimide of the present embodiment. For example, it may be a subtractive method in which a metal-clad laminate comprising an insulating resin layer containing the thermoplastic polyimide of the present embodiment and a metal layer is prepared, and the metal layer is etched to form a wiring. Further, a semi-additive method may be employed in which a seed layer is formed on a layer of the thermoplastic polyimide of the present embodiment, and then a resist is patterned to further pattern the metal. Wiring is formed.

<Operation> The diamine (1) to the diamine (7) used as a monomer in the present embodiment have high flexibility, can improve the flexibility of the polyimine molecular chain, and can impart high thermoplasticity. Further, since the diamine (8) has a rigid structure, it has an effect of imparting an ordered structure to the entire polymer. When such an ordered structure is formed, not only the dielectric loss tangent can be suppressed, but also the transmission of gas such as oxygen, which is a main factor for the long-term heat-resistant adhesion to the metal wiring layer, is suppressed. Therefore, by using one or more kinds of diamines (1) to diamines (7) and one or more kinds of diamines (8) in combination at a predetermined ratio, it is obtained as a thermoplastic resin, but not only a low medium can be used. A polyimine which has a low electrical loss and a low gas permeability and excellent long-term heat-resistant adhesion. As described above, although it is thermoplastic and has high adhesiveness, the polyimine which exhibits excellent long-term heat-resistant adhesion by the low gas permeability due to the ordered structure is first realized by the present invention. Further, the degree of formation of the ordered structure of the polyimine can be estimated from the change in the total light transmittance and the haze in the state of film formation as shown in the examples below.

As described above, since the polyimide of the present embodiment is thermoplastic, it has excellent adhesion to a low-roughness copper foil. Further, although the polyimine of the present embodiment is thermoplastic, an ordered structure is formed in the entire polymer by a rigid structure derived from a monomer, so that not only low dielectric loss tangent but also gas permeability can be reduced. Sex, with excellent long-term heat-resistant adhesion. Therefore, the resin film having the adhesive layer formed using the thermoplastic polyimide of the present embodiment is excellent in adhesion to the metal wiring layer, and can be used as an electronic component such as an FPC for manufacturing high-density mounting or high reliability. The materials are used properly. Example

The embodiments are described below to more specifically explain the features of the present invention. However, the scope of the invention is not limited to the embodiments. In addition, in the following examples, unless otherwise indicated, various measurement and evaluation are based on the following.

[Measurement of Viscosity] The viscosity was measured by using an E-type viscometer (manufactured by Brookfield, trade name: DV-II+Pro) to measure the viscosity at 25 °C. The number of revolutions was set so that the torque became 10% to 90%, and after the measurement was started, the value at the time when the viscosity was stabilized was read after 2 minutes passed.

[Measurement of Weight Average Molecular Weight] The weight average molecular weight was measured by gel permeation chromatography (manufactured by Tosoh Corporation, trade name: HLC-8220GPC). Polystyrene was used as a standard material, and N,N-dimethylacetamide was used in the developing solvent.

[Measurement of Surface Roughness of Copper Foil] The surface roughness of the copper foil is Atomic Force Microscope (AFM) (Brook AXS (manufactured by Bruker AXS), trade name: Dimension Icon type SPM), and probe (Brook) Manufactured by AXS (Bruker AXS), trade name: TESPA (NCHV), front radius of curvature 10 nm, spring constant 42 N/m), in tapping mode, 80 μm × 80 μm on the surface of copper foil The range was measured, and the ten-point average roughness (Rz) was obtained.

[Measurement of Peel Strength] 1) Casting side of the single-sided copper-clad laminate (resin-coated side) Copper foil of a single-sided copper-clad laminate (copper foil/resin layer) was circuit-processed to have a width of 1.0 mm After the line and space of 5.0 mm were separated, the width was cut: 8 cm × length: 4 cm, and the measurement sample 1 was prepared. The peeling strength of the casting side of the measurement sample 1 was measured by the following method. Using a Tensilon tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Strograph VE-1D), the resin layer side of the measurement sample 1 was fixed to an aluminum plate by a double-sided tape, and the copper foil was 90. The peeling was performed at a speed of 50 mm/min in the direction of °, and the center strength when the copper foil was peeled off from the resin layer by 10 mm was determined. This value is referred to as "peel strength 1A".

2) Casting side (resin-coated side) of the double-sided copper-clad laminate. The hot-pressed side of the double-sided copper-clad laminate (copper foil/resin layer/copper foil) and the copper foil on both sides of the casting side are respectively subjected to The circuit is machined to a line and space with a width of 0.8 mm and a spacing of 3.0 mm. Here, the circuit processing of the copper foil on both sides is performed such that the position of the line and the space overlap on both sides of the front and back sides. The sample subjected to the circuit processing as described above was cut into a width: 8 cm × length: 4 cm, and a measurement sample 2 was prepared. The peeling strength of the casting side of the measurement sample 2 was measured by the following method. Using a Tensilon tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Strograph VE-1D), the copper foil side of the thermocompression bonding side of the measurement sample 2 was fixed to the aluminum plate by double-sided tape. The copper foil was peeled off at a speed of 50 mm/min in the direction of 90°, and the central value of the copper foil on the resin-coated side was peeled off from the resin layer by 10 mm. This value is referred to as "peel strength 2A".

[Measurement of heat-resistant peel strength] 1) Casting side of one-side copper-clad laminate (resin-coated side) The measurement sample 1 prepared as described above was placed in an air oven at 150 ° C and allowed to stand for 1000 hours. The resin layer side of the measurement sample 1 after heat treatment for 1000 hours was fixed to an aluminum plate by a double-sided tape, and the copper foil was peeled off at a speed of 50 mm/min in a 90° direction, and the copper foil was peeled off from the resin layer. The central strength at 10 mm. This value is referred to as "peel strength 1B". The percentage (%) of the value obtained by dividing the peel strength 1B by the peel strength 1A (that is, the peel strength 1B/peel strength 1A) was defined as "retention ratio 1". <Criteria for Judgment> "Excellent": The peel strength 1B is 0.30 kN/m or more, and the retention ratio 1 is 80% or more. "Good": The peel strength 1B is 0.30 kN/m or more, and the retention ratio 1 is 60% or more. "可可": The peel strength 1B is 0.30 kN/m or more, and the retention ratio 1 is 40% or more. "Not available": Peel strength 1B is less than 0.30 kN/m.

2) Casting side of the double-sided copper-clad laminate (resin-coated side) The measurement sample 2 prepared in the manner described above was placed in an atmospheric oven at 177 ° C and allowed to stand for 240 hours. The copper foil surface on the thermocompression bonding side of the measurement sample 2 after the heat treatment for 240 hours was fixed to the aluminum plate by the double-faced tape, and the copper foil was peeled off at a speed of 50 mm/min in the 90° direction to obtain a resin coating. The copper foil on the side of the coating was peeled off from the resin layer by a central value of 10 mm. This value is referred to as "peel strength 2B". The percentage (%) of the value obtained by dividing the peel strength 2B by the peel strength 1B (that is, the peel strength 2B/peel strength 2A) was defined as "retention ratio 2". <Criteria for Judgment> "Excellent": The peel strength 2B is 0.50 kN/m or more, and the retention ratio 2 is 90% or more. "Good": The peel strength 2B is 0.50 kN/m or more, and the retention ratio 2 is 80% or more. "Yes": The peel strength 2B is 0.50 kN/m or more, and the retention ratio 2 is 70% or more. "Not available": Peel strength 2B is less than 0.50 kN/m, or retention ratio 2 is less than 70%.

[Measurement of glass transition temperature (Tg)] For a sample of a polyimide film having a size of 5 mm × 20 mm, a dynamic viscoelasticity measuring device (DMA: manufactured by UBM, trade name: E4000F) was used, from 30 ° C to The storage elastic modulus and the loss elastic modulus were measured at a temperature increase rate of 4 ° C/min and a frequency of 11 Hz at 400 ° C, and the temperature at which the elastic modulus change (tan δ ) was maximized was defined as the glass transition temperature. Further, the storage elastic modulus at 30 ° C is 1.0 × 10 ⁹ Pa or more, and the storage elastic modulus at 360 ° C is less than 1.0 × 10 ⁸ Pa, which is "thermoplastic", and the storage elastic modulus at 30 ° C is used. The number is 1.0 × 10 ⁹ Pa or more, and the storage elastic modulus at 360 ° C shows that 1.0 × 10 ⁸ Pa or more is "non-thermoplastic".

[Visibility] For the sample in which the polyimide film was cut into a thickness of about 25 μm and 30 mm × 30 mm, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: HAZE METER NDH5000) was used. ), the total light transmittance and haze (turbidity = diffused light transmittance / total light transmittance) according to JIS K7136 were measured.

[Measurement of Dielectric Constant and Dielectric Loss Tangent] Using a vector network analyzer (Agilent, trade name E8363C) and a Split Post Dielectric Resonator (SPDR resonator) The dielectric constant and dielectric loss tangent of the polyimide film at a frequency of 10 GHz were measured. Further, the polyimide film used for the measurement was placed at a temperature of 24 ° C to 26 ° C and a humidity of 45% to 55% for 24 hours.

The abbreviations used in the examples and comparative examples indicate the following compounds. m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl PDA: p-phenylenediamine APAB: 4-aminophenyl-4'-aminobenzoate MABA: 2 '-Methoxy-4,4'-diaminobenzimidamide TPE-R: 1,3-bis(4-aminophenoxy)benzene APB: 1,3-bis(3-aminobenzene Oxy)benzene TPE-Q: 1,4-bis(4-aminophenoxy)benzene BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane PMDA: Benzene Tetracarboxylic acid dianhydride BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride DMAc: N,N-dimethylacetamide copper foil: Rz=0.35 μm, thickness 12 μm

[Example 1] 0.5715 g of m-TB (0.0027 mol), 14.958 g of TPE-R (0.0512 mol), and 170 g of DMAc were placed in a 300 ml separable flask under a nitrogen stream. Stir at room temperature to dissolve. Then, after adding 3.489 g of PMDA (0.0160 mol) and 10.982 g of BPDA (0.0373 mol), the mixture was further stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyproline solution a. The polyaminic acid solution a had a solution viscosity of 6,700 cps and a weight average molecular weight of 163,400.

[Example 2 to Example 12] The polyamic acid solutions b to k and m were prepared in the same manner as in Example 1 except that the raw material compositions shown in Tables 1 and 2 were used to measure the viscosity.

[Table 1]

[Table 2]

Synthesis Example 1 In a 300 ml separable flask, 16.064 g of TPE-R (0.0550 mol) and 170 g of DMAc were placed under a nitrogen stream, and stirred at room temperature to dissolve. Then, after adding 5.933 g of PMDA (0.0272 mol) and 8.03 g of BPDA (0.0272 mol), the mixture was further stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyproline solution n. The solution viscosity of the polyaminic acid solution n was 7,400 cps.

Synthesis Example 2 to Synthesis Example 6 Polyacetamide solutions o to s were prepared in the same manner as in Synthesis Example 1 except that the raw material compositions shown in Table 3 were used to measure the viscosity.

[table 3]

[Example 13] On the copper foil, the polyamic acid solution c was uniformly applied so as to have a thickness of about 2 μm after the heat treatment, and the mixture was heated and dried at 120 ° C for 1 minute to remove the solvent. The polyamic acid solution s was uniformly applied thereto so as to have a thickness of about 25 μm after the heat treatment, and dried by heating at 120 ° C for 3 minutes to remove the solvent. Then, the temperature was raised from the temperature of 130 ° C to 360 ° C in a stepwise manner, and hydrazine imidization was carried out to prepare a single-sided copper-coated laminate 1 . The evaluation results of the one-sided copper-clad laminate 1 are shown in Table 4.

[Example 14] A single-sided copper-coated laminate 2 was prepared in the same manner as in Example 13 except that the polyamic acid solution d was used instead of the polyamic acid solution c. The evaluation results of the one-sided copper-clad laminate 2 are shown in Table 4.

[Example 15] A single-sided copper-clad laminate 3 was prepared in the same manner as in Example 13 except that the polyamic acid solution j was used instead of the polyamic acid solution c. The evaluation results of the one-sided copper-clad laminate 3 are shown in Table 4.

Comparative Example 1 A single-sided copper-coated laminate 4 was prepared in the same manner as in Example 13 except that the polyamic acid solution c was used instead of the polyamic acid solution c. The evaluation results of the one-sided copper-clad laminate 4 are shown in Table 4.

Comparative Example 2 A single-sided copper-coated laminate 5 was prepared in the same manner as in Example 13 except that the polyamic acid solution c was used instead of the polyamic acid solution c. The evaluation results of the one-sided copper-clad laminate 5 are shown in Table 4.

Comparative Example 3 A single-sided copper-coated laminate 6 was prepared in the same manner as in Example 13 except that the polyamic acid solution p was used instead of the polyamic acid solution c. The evaluation results of the one-sided copper-clad laminate 6 are shown in Table 4.

Comparative Example 4 A single-sided copper-coated laminate 7 was prepared in the same manner as in Example 13 except that the polyamic acid solution q was used instead of the polyamic acid solution c. The evaluation results of the one-sided copper-clad laminate 7 are shown in Table 4.

[Table 4]

[Example 16] The polyamic acid solution a was uniformly applied to the copper foil so that the thickness after hardening became about 2 μm, and then dried by heating at 120 ° C for 1 minute to remove the solvent. On the other hand, the polyamic acid solution s was uniformly applied so that the thickness after hardening became about 18 μm, and then dried by heating at 120 ° C for 3 minutes to remove the solvent. Further, the polyamic acid solution a was uniformly applied so as to have a thickness of about 2 μm after hardening, and then dried by heating at 120 ° C for 1 minute to remove the solvent. Then, a stepwise heat treatment is performed from 130 ° C to 360 ° C to complete the hydrazine imidization, and a single-sided copper-coated laminate 8 is prepared. The copper foil was placed on the side of the polyimide layer of the single-sided copper-clad laminate 8 and thermocompression bonded at a temperature of 310 ° C and a pressure of 6.7 MPa for 15 minutes to prepare a double-sided copper-clad laminate 8. The evaluation results of the double-sided copper-clad laminate 8 are shown in Table 5.

[Example 17] A single-sided copper-clad laminate 9 and a double-sided copper-clad laminate 9 were prepared in the same manner as in Example 16 except that the polyamic acid solution b was used instead of the polyamic acid solution a. The evaluation results of the double-sided copper-clad laminate 9 are shown in Table 5.

[Example 18] A single-sided copper-clad laminate 10 and a double-sided copper-clad laminate 10 were prepared in the same manner as in Example 16 except that the polyamic acid solution c was used instead of the polyamic acid solution a. The evaluation results of the double-sided copper-clad laminate 10 are shown in Table 5.

[Example 19] A single-sided copper-coated laminate 11 was prepared in the same manner as in Example 16 except that the polyamic acid solution e was used instead of the polyamic acid solution a. Further, a double-sided copper-clad laminate 11 was produced in the same manner as in Example 16 except that the single-sided copper-clad laminate 11 was used and thermocompression bonding was carried out for 15 minutes under the conditions of a temperature of 330 ° C and a pressure of 6.7 MPa. The evaluation results of the double-sided copper-clad laminate 11 are shown in Table 5.

[Example 20] A single-sided copper-clad laminate 12 and a double-sided copper-clad laminate 12 were prepared in the same manner as in Example 16 except that the polyamic acid solution a was used instead of the polyamic acid solution a. The evaluation results of the double-sided copper-clad laminate 12 are shown in Table 5.

[Example 21] A single-sided copper-clad laminate 13 and a double-sided copper-clad laminate 13 were prepared in the same manner as in Example 16 except that the polyamic acid solution g was used instead of the polyamic acid solution a. The evaluation results of the double-sided copper-clad laminate 13 are shown in Table 5.

[Example 22] A single-sided copper-coated laminate 14 was prepared in the same manner as in Example 16 except that the polyamic acid solution h was used instead of the polyamic acid solution a. Further, a double-sided copper-clad laminate 14 was produced in the same manner as in Example 16 except that the single-sided copper-clad laminate 14 was used and thermocompression bonding was carried out for 15 minutes under the conditions of a temperature of 330 ° C and a pressure of 6.7 MPa. The evaluation results of the double-sided copper-clad laminate 14 are shown in Table 5.

[Example 23] A single-sided copper-clad laminate 15 and a double-sided copper-clad laminate 15 were prepared in the same manner as in Example 16 except that the polyamic acid solution i was used instead of the polyamic acid solution a. The evaluation results of the double-sided copper-clad laminate 15 are shown in Table 5.

Comparative Example 5 A single-sided copper-clad laminate 16 was prepared in the same manner as in Example 16 except that the polyamic acid solution q was used instead of the polyamic acid solution a. Further, a double-sided copper-clad laminate 16 was produced in the same manner as in Example 16 except that the single-sided copper-clad laminate 16 was used and thermocompression bonding was carried out for 15 minutes under the conditions of a temperature of 390 ° C and a pressure of 6.7 MPa. The evaluation results of the double-sided copper-clad laminate 16 are shown in Table 5.

Comparative Example 6 A single-sided copper-coated laminate 17 was prepared in the same manner as in Example 16 except that the polyamic acid solution r was used instead of the polyamic acid solution a. Further, a double-sided copper-clad laminate 17 was produced in the same manner as in Example 16 except that the single-sided copper-clad laminate 17 was used and thermocompression bonding was carried out for 15 minutes under the conditions of a temperature of 350 ° C and a pressure of 6.7 MPa. The copper foil on the thermocompression bonding side of the double-sided copper-clad laminate 17 can be easily peeled off by hand, and the circuit processing of the copper foil on the thermocompression bonding side cannot be performed.

[table 5]

[Example 24] The polyamic acid solution a was uniformly applied onto a copper foil, and dried by heating at 120 ° C for 3 minutes to remove the solvent so that the thickness after the heat treatment was about 25 μm. Then, the temperature was raised from 360 ° C to 360 ° C in a stepwise manner, and hydrazine imidization was carried out to prepare a single-sided copper-coated laminate 18 . The polyimide film 18 is prepared by etching away the copper foil of the single-sided copper-clad laminate 18. The evaluation results of the polyimide film 18 are shown in Table 6.

[Examples 25 to 33] Polyimine films 19 to 27 were prepared in the same manner as in Example 24 except that the polyamic acid solutions b to j were used. The evaluation results of the polyimide films 19 to 27 are shown in Table 6.

[Table 6]

[Example 34] The polyamic acid solution a was uniformly applied to the copper foil so that the thickness after hardening became about 2 μm, and then dried by heating at 120 ° C for 1 minute to remove the solvent. On the other hand, the polyamic acid solution s was uniformly applied so that the thickness after hardening became about 18 μm, and then dried by heating at 120 ° C for 3 minutes to remove the solvent. Further, the polyamic acid solution a was uniformly applied so as to have a thickness of about 2 μm after hardening, and then dried by heating at 120 ° C for 1 minute to remove the solvent. Then, a stepwise heat treatment is performed from 130 ° C to 360 ° C to complete the hydrazine imidization, and a single-sided copper-coated laminate 28 is prepared. The polyimide film 28 is prepared by etching away the copper foil of the single-sided copper-clad laminate 28. The total light transmittance in the polyimide film 28 was 73%, and the haze was 54%.

[Example 35] A polyimide film 29 was prepared in the same manner as in Example 34 except that the polyamic acid solution f was used instead of the polyamic acid solution a. The polyimide film 29 had a total light transmittance of 74% and a haze of 56%.

[Example 36] A polyimide film 30 was prepared in the same manner as in Example 34 except that the polyamic acid solution g was used instead of the polyamic acid solution a. The polyimide film 30 had a total light transmittance of 74% and a haze of 55%.

[Reference Example 1] A polyimide film 31 was prepared in the same manner as in Example 34 except that the polyamic acid solution q was used instead of the polyamic acid solution a. The polyimide film 31 had a total light transmittance of 77% and a haze of 50%.

[Example 37] A polyimide film 32 was prepared in the same manner as in Example 24 except that the polyamic acid solution k was used. The polyimide film 32 has a dielectric constant of 3.40 and a dielectric loss tangent of 0.0032.

[Example 38] A polyimide film 34 was prepared in the same manner as in Example 24 except that the polyamic acid solution m was used. The polyimide film 34 had a dielectric constant of 3.52 and a dielectric loss tangent of 0.0037.

Comparative Example 7 A polyimide film 35 was prepared in the same manner as in Example 24 except that the polyamic acid solution q was used. The polyimide film 35 had a dielectric constant of 3.16 and a dielectric loss tangent of 0.0057.

The embodiments of the present invention have been described in detail above for the purpose of illustration. However, the present invention is not limited by the embodiments.

The present application claims priority to Japanese Patent Application No. 2016-54299, filed on Jan.

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no

Claims (6)

A polyaminic acid obtained by reacting a diamine component with an anhydride component, wherein the polyamine component is characterized in that the diamine component contains a total of 100 moles of all diamine components. It is at least one selected from the group consisting of the diamine compounds represented by the following general formulae (1) to (7) in a range of from 40 mole parts to 97 mole parts, and a total of from 3 moles to 60 moles. At least one selected from the group consisting of diamine compounds represented by the following formula (8) in the range of the ear portion, and the acid anhydride component contains 40 mol parts to 100 parts per 100 mol parts of the entire acid anhydride component. Biphenyltetracarboxylic dianhydride in the range of moles, and pyromellitic dianhydride in the range of 0 moles to 60 moles, In the formulae (1) to (7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms; and the linking group A independently represents a group selected from -O-, -S-, -CO-, a divalent group in -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-; n ₁ independently represents an integer of 0 to 4 Wherein, except in the formula (3) and the formula (2), except in the formula (5), except for the formula (4), In the formula (8), the linking group X represents a divalent group selected from a single bond or -CONH-; Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms or an alkoxy group; and n represents 0 to 2 An integer; p and q independently represent an integer from 0 to 4. A thermoplastic polyimine comprising a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from an anhydride component, the thermoplastic polyimine characterized by: relative to all diamine residues 100 mol parts, which are derived from at least one selected from the group consisting of diamine compounds represented by the following general formulae (1) to (7) in a range of from 40 mol parts to 97 mol parts in total. a diamine residue, and a diamine residue selected from at least one of the diamine compounds represented by the following formula (8) in a total range of from 3 mole parts to 60 mole parts, and relative to all 100 mole parts of the tetracarboxylic acid residue, containing 40 moles to 100 moles of tetracarboxylic acid residues derived from biphenyltetracarboxylic dianhydride, and 0 moles to 60 moles a tetracarboxylic acid residue derived from pyromellitic dianhydride in the range of the ear, In the formulae (1) to (7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms; and the linking group A independently represents a group selected from -O-, -S-, -CO-, a divalent group in -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-; n ₁ independently represents an integer of 0 to 4 Wherein, except in the formula (3) and the formula (2), except in the formula (5), except for the formula (4), In the formula (8), the linking group X represents a divalent group selected from a single bond or -CONH-; Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms or an alkoxy group; and n represents 0 to 2 An integer; p and q independently represent an integer from 0 to 4. A resin film having a single layer or a plurality of layers of a polyimide film, the resin film being characterized in that at least one layer of the polyimide layer contains the thermoplastic polymer as described in claim 2 Imine. A metal-clad laminate comprising an insulating resin layer and a metal layer, the metal-clad laminate being characterized in that the insulating resin layer has a single layer or a plurality of layers of polyimine, and the metal layer The contacted polyimide layer comprises the thermoplastic polyimine as described in claim 2 of the patent application. The metal-clad laminate according to claim 4, wherein the metal layer of the surface in contact with the insulating resin layer has a ten-point average roughness (Rz) of 0.05 μm to 1.0 μm. A circuit board obtained by processing the metal layer of the metal-clad laminate according to item 4 of the above application.